Noninnocent Counterion Effect on the Rearrangements of Cationic Intermediates in a Gold(I)-Catalyzed Alkenylsilylation Reaction

A mechanistic DFT study of the gold(I)-catalyzed alkenylsilylation reaction of a silyl-tethered 1,6-enyne system is reported. A novel pathway involving bistriflimide counterion-assisted rearrangements of carbocation and silyl cation intermediates corroborates the experimental observations. The results suggest the important role of the counterion in modulating the reactivity of cationic intermediates in gold catalysis.